Homologues of isoionone and process of making same.



No. 762,765. Patented June 14, 1904.

UNITED STATES PATENT OFFICE.

RICHARD SCHMIDT, OF I-IOLZMINDEN, GERMANY, ASSIGNOR, BY MESNE ASSIGNMENTS, TO HAARMANN & REIMER, CHEMISCHE FABRIK ZU HOLZMINDEN, G. M. B. H., OF HOLZMINDEN, GERMANY, A FIRM.

HOIVIOLOGUES OF ISQIONONE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 762,765, dated June 14, 1904.

Application filed August 23, 1901. Serial No. 73,026. (Specimens) To who??? it y 00710072 methylethyl-ketone, and to this mixture five Be it known that I, RICHARD SCHMIDT, a parts of sodium dissolved in the requisite 5 subject of the Duke of Brunswick, doctor of quantity of alcohol are added. The mixture philosophy, chemist, and a resident of HolZ- is left at the ordinary temperature for an minden, in the Duchy of Brunswick, German hour or two or more, if necessary, until the Empire, have invented certain new and useful odor of cyclo citral has disappeared. The Homologues of Isoionone and Process of Makmixture is then acidified slightly with a soluing the Same, of which the following is a speci tion of some weak acid, such as tartaric acid, fication. and is distilled in steam, which carries over IO In Haarmann & Reimers German Patent first all excess of the methylethyl-ketone and No. 116,637 it has been shown that ionone finally the methylionone. may be obtained by condensing cyclo-citral When a mixture of alpha and beta cycloand acetone by means of alkaline agents. citral is used, a mixture of alpha and beta I have found that the alpha and beta hornomethylionone is obtained. These are sepa- 5 logues of ionone may be prepared directly by rated by meansof their semicarbazones, and condensing the homologues of acetone with the homoionones are then produced by the the different cyclo-citrals. Thus I may use, action of dilute acids in the known manner. 5 for instance, the crude cyclo-citral described By using pure alpha cyclo-citral there is obin Strebels German Patent N 0. 108,335 or obtained alpha methylionone, while by using 20 tained by any modification of the process pure beta cyclo-citral I obtain beta-methyltherein described. The productderived from ionone. These homoionones have the followthis cyclo-citral is a mixture of alpha and beta ing characteristics: 7 homoionones, which may be separated by Alpha-methylionone boils at 140 to 155 means of their semicarbazones. The beta cycentigrade under twenty millimeters pressure 5 clo-citral, which exists in large proportion in (not corrected) and has a specific gravity of crudecyclo-citral and may beisolated bymeans 0.925 to 0.931 at 20 centigrade, the refractof its semicarbazone, may also be used. In ing-index being aD 1.501.51. this case beta-homoionones are obtained. Fi Beta-methylionone boils at 140 to 150 nally, to prepare alpha-homoionones one may centigrade under twenty millimeters pressure 3 start with the alpha cyclo-citral isolated from (not corrected) and has a specific gravity of crude cyclo-citral by means of a suitable hy- 0.935 to 0.940 at 20 centigrade,the refractingdrogenizing agent, likesodium amalgam and index being m =1.501.52. The distinguishacetic acid, which transforms the beta cyclo-ciing characteristics of the dimethyl substitutral into a substance of very high boiling-point j tion products of ionone obtained by my proc- 35 and melting at 129 centigrade, but leaves the ess are the following: alpha-dimethylionone,

alpha cyclo-citral unchanged, which is sepaboiling-point 145 to 160 under twenty milrated by distillation with steam. Alpha cylimeters pressure, specific gravity 0.915 to 5 clo-citral has been found to possess a boiling- 0.924 at 20 refracting-index 1w=l.49-1.50; point of from to centigrade (mercury beta dimethylionone, (dimethylis'oionone,) 4 column in vapor) and a specific gravity of boilingpointto under twenty milli- 0.925 to 0.930. Its semicarbazone melts at meters pressure, specific gravity0. 927 to0.935

204 to 206 at 18 refracting-index m) 1.511.52. In 9 The present invention relates to the manua similar manner the pure alpha cyclo-citral facture of homologues of alpha and beta ioor the pure beta cyclo-citral may be condensed 45 none in the manner indicated above and is not only with the other ordinary homologues illustrated by the following example: of acetone, but with unsaturated ketones,

Example: Fifty parts of crude or pure cysuch as mesityloxid, methyl-heptenones, and 95 clo-citral are mixed with one hundredparts of the like. The products obtained in this manner from mesityloxid are these: alpha pro penyl-ionone, boiling at 155 to 165 centigr-ade under fifteen millimeters pressure, (not corrected,) specific gravity 0.935 to 0.940 at 20 centigrade, refracting-index about 1.52; and beta propenyl-ionone, boiling at 160 to 17 2 centigrade at fifteen millimeters pressure, specific gravity 0. 9&0 to 0.945 at 2O. centigrade, refracting-index about 1.53.

I am aware that it is old to form a condensation product called ionone of the ketone series from cyclo-citral and acetone; and I am also aware of the splitting up of commercial ionone and of its homologues, which latter were heretofore obtained from the aliphatic aldehydes and ketones by condensation with alkali and subsequent conversion with acid into an alpha and a beta series; but as far as 1 am aware I am the first to devise a method for manufacturing homo cyclic ionones and their alpha and beta isomers directly from ordinary commercial cyclo-citral.

What I claim, and desire to secure by Letters Patent of the United States, is

1. The process herein described for manucyclo-citral, these products being homologues of cyclic beta or iso ionone possessing the odor of violets and orris and having the physical and chemical characteristics herein set forth.

In witness whereof I have hereunto signed my name in the presence of two subscribing witnesses.

RICHARD SCHMIDT. Witnesses:

WOLDEMAR HAUPT, v HENRY HASPER. 

